Electrochemical and Analytical Perspectives on Lithium Diffusion in Silicon and Graphite Anodes for Next‐Generation Batteries

This study provides a detailed look at how lithium ions move in silicon and graphite anodes using different electrochemical and analytical methods. Lithium diffusion controls how ions move inside the electrode. This movement directly affects the battery's energy, lifetime, and safety. Among anode materials, graphite and silicon stand out due to their high specific capacities and outstanding electrochemical properties. However, anisotropic diffusion in graphite and substantial volume expansion in silicon complicate diffusion kinetics and lead to mechanical degradation. The study carefully examines four main techniques: cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic intermittent titration technique (GITT), and potentiostatic intermittent titration technique (PITT). Each method is analyzed for its theory, experimental conditions, and how reliable its measurements are. Diffusion coefficients ( D Li+ ) range from 10 −11 –10 −9 cm 2 /s for graphite and 10 −13 –10 −11 cm 2 /s for silicon, with variations attributed to electrode morphology, solid electrolyte interphase (SEI) evolution, and model limitations reported in literature. Current limitations, including nonideal geometries, irreversible reactions, and a lack of standardized data reporting, restrict comparability across studies. Future progress requires standardized testing protocols, the integration of operando characterization techniques to monitor real‐time diffusion, and advanced chemo‐mechanical or multiscale modeling approaches. These advancements will improve the accuracy of D Li+ measurement and facilitate the design of robust, high‐capacity anodes for next‐generation lithium‐ion batteries.